Azo dyestuffs soluble in water



Patented Oct. 10, 1939 UNITED STATES PATENT OFFICE AZO DYESTUFFS SOLUBLE IN WATER Erich Fischer and Walter Gmelin, Bad Soden in Taunus, and Richard Huss, Frankfort-on-the- Main-Hochst, Germany, assignors to General Aniline Works, Inc., New York, N. Y., a corporation of Delaware N Drawing. Application March 19, 1938, Se-

rial No. 196,900. In Germany March 23, 1937 4 Claims. (01. 260-198) The present invention relates to azo-dyestuffs with good exhaustion of the dye-bath. The dyesoluble in water; more particularly, it relates to stuif corresponds with the following formula:

dyestuffs of the following general formula: H

N=N N 5 N/ \OH CH so 11 5 My Xenia-sole HO X 2. If in Example 1 the aminobenzene is exchanged for 123 parts of 1-amino-2-methoxybenggelrpeln X stands for hydrogen or a SulfOmc acld zene, a dyestuff of similar properties is obtained.

' 3. 203 parts of 1-amino-4-methoxybenzene-2- 15 We i found that Valuable sulfonic acid are diazotised in the usual manner 15 solubl? m Water are 9btaina'b1e by combmmg and coupled with an aqueous solution of 253 any dlazo'compound wlth droxy" parts of 1sulfethylamino-7-hydroxynaphthalene naphthalene of the general constitution: and 212 parts of Sodium carbonate. The H stuff is salted out, filtered with suction and dried.

It is a black powder which dyes leather through- 20 out grey-black shades. OH\ film-803E 4. 123 parts of l-aminol-methoxybenzene (molecular weight 123) are diazotised in the usual manner at 0 C.-3 C. in the presence of hydrochloric acid in excess with 69 parts of 25 sodium nitrite. The diazo-solution is then wherein the naphthalene nucleus may contain a caused to run tirring into an aqueous further Sulfonic acid groupsolution, cooled to 0 0., of 410 parts of the di- The dyestuffs thus obtained have the valuable Sodium salt of 1... u1fethy1amjno 7..hydrox aph property of dyeing leather in the grain thalene-4-sulfonic acid (molecular weight 391, 30 throughout shades extending from violet to blue obtainable by condensing 7 black- AS far as diam-Compounds 0f the naphthalene4-sulfonic acid with sodium chlorbenzene series are used for the manufacture of tha sulf at in the presence of an acidthe dyestuffs and the finished dyestuffs contain binding agent), in the presence of 5 parts of besides the alkyl-SOzH-group no further sulfonic anhydrous odium carbonate The dyestufi the acid group, the dyestuffs are particularly p formation of which is very quickly completed, is ed for dyeing W001 from an acid bath below isolated in the usual manner and dried. It is a boiling temperature, the dyerbaths being Suffiblack powder which dissolves in water to a greyc y y W811 exhaustedviolet solution and is, for instance, very suitable o The following examples serve to illustrate the for dyeing l th 40 invention, bu y e not intended to limit it Chrome-tanned velvet-leather is well drummed th e t e pa ts are y Weight: before dyeing. It is then dyed in a fresh bath 1. Into a solution obtained from 253 parts of t 3 per cent, of t above dyestufi" calcu- 1 Sulfethylamino 7 hydroxynaphthalene lated upon the dry-weight of the leather. After tainable by condensing 2 hours dyeing, 4 per cent. of formic acid are 45 thalene with sodium chlorethanesulfonate in the d n dd d and th leather is further presence of all acid-binding agent), Water and drummed for one hour. It is then thoroughly 212 parts of sodium carbonate there is introrin d nd dried. The leather is dyed in the duced a diazo-solution obtained in the usual grain ey-vi let tints and may, therefore, well manner from 93 parts of aminobenzene. When b buffed, 50 the coupling is complete, the dyestuif is salted 5. 173 parts of 1-aminobenzene-4-sulfonic acid out from the solution in the usual way, filtered are diazotised in the presence of 150 parts of with suction and dried. It dyes leather in the concentrated hydrochloric acid with 69 parts of grain grey-black tints. Furthermore it dyes sodium nitrite. The diazo-compound is then wool in an acid bath below boiling temperature gradually introduced into an aqueous solution, 55

cooled to 0 C., of 253 parts of 1-sulfethylamino- 7-hydroxynaphthalene to which there have been added 159 parts of sodium carbonate. The dyestuff thus obtained is separated in the usual manner by means of sodium chloride, filtered with suction and dried. It is a black powder which dyes leather throughout grey-black tints.

6. If in Example 5 the l-aminobenzenelsulfonic acid is exchanged for 187 parts of para amincbenzylsulfonic acid, a black dyestuff is obtained which likewise dyes leather throughout grey-black tints.

7. A dyestuff dyeing leather throughout greyblack tints is obtained by combining a diazosolution, prepared in the usual manner from 310 parts of 4 amino-2-sulfophenylmethyltaurine, with a solution of 253 parts of l-sulfethylamino- 7-hydroxynaphthalene in the presence of sodium carbonate in excess.

8. A diazo-solution from 151 parts of l-aminobenzene-3-carboxy1ic acid methyl-ester is run at 0 G. into a solution of 253 parts of l-sulfethylamino-7-hydroxynaphthalene rendered alkaline by means of sodium carbonate. The dyestuif thus obtained is isolated in the usual manner and dried. It is a black powder which dyes leather black tints fast to buffing.

9. A dyestuif dyeing leather in the grain black tints is obtained by diazotising 230 parts of paraaminosulfacetanilide in the usual manner and combining the diaZo-solution in the presence of sodium carbonate in excess with a solution of 253 parts of l-sulfethylamino-'7-hydroxynaphthalene.

10. 218 parts of 1-amino-2-nitrobenzene-2-solfonic acid are diazotised in the usual manner and the diazo-solution is combined, while vigorously stirring, at 0 C. in the presence of 250 parts of anhydrous sodium carbonate with an aqueous solution of 390 parts of the disodium salt of l-sulfomethylamino-7-hydroxynaphthalene-3-sulfonic acid (molecular weight 3'77, obtainable by the action of formaldehyde bisulfite on an aqueous solution of the sodium salt of l-amino-7-hydroxynaphthalene-3sulfonic acid at 50 C. to 60 C.). The dyestuff is separated by means of potassium chloride, filtered with suction and dried. It is a black powder which dissolves in water to a greyviolet solution.

The dyestuff dyes leather reddish grey tints which may well be buffed and used for velvet effects.

11. A diazo-solution obtained in the usual manner from 172.5 parts of 4-chloro-2-nitro-1-aminobenzene is run, while stirring, at 0 C. into an aqueous solution of 390 parts of the disodium salt of 1-sulfomethylamino-7-hydroxynaphthalene-3- sulfonic acid (molecular weight 377) and 250 parts of anhydrous sodium carbonate. When the formation of the dyestufi is complete, it is separated by means of sodium chloride, filtered with suction and dried. There is obtained a black powder which dissolves in water to a grey-violet solution. The product is suitable for dyeing leather grey tints which may well be buffed.

12. 172.5 parts of 2-ch1oro-4-nitro-1-aminobenzene are diazotised in the usual manner and combined at 0 C., while vigorously stirring, with an aqueous solution of 390 parts of the disodium salt of l-sulfomethylamino-7-hydroxynaphthalene-3-sulfonic acid. and 250 parts of anhydrous sodium carbonate. When the formation of the dyestuff is complete, it separates in a form easily to be filtered. The dried dyestuff is a black powder which dissolves in water to a violet-grey solution and dyes leather in the grain greenish grey tints.

13. 299 parts of sodium 4-aminoazobenzene-4- sulfonate are diazotised in the usual manner in the presence of hydrochloric acid in excess with 69 parts of sodium nitrite. The diam-compound obtained is slowly introduced, while well stirring, at 0 C.-3 C. into an aqueous solution of 390 parts of the disodium salt of l-sulfomethylamino- 7-hydroxynaphthalene-3-sulfonic acid and 200 parts of anhydrous sodium carbonate. When the formation of the dyestuff is complete, it is separated by means of sodium chloride, filtered with suction and dried. It is a black powder which dissolves in water to a grey-violet solution. The dyestufi yields on leather black tints fast to buffing.

We claim:

1. The water-soluble azo-dyestuffs of the following general formula:

wherein R stands for a radical of the benzene series, X for one of the group consisting of hydrogen and the sulfonic acid group and Y for one of the group consisting of methyl and ethyl, being dark powders which penetrate deeply into the leather and yield shades extending from violet to blue to black.

2. The water-soluble azo-dyestuff of the following formula:

being a black powder which dyes leather throughout grey-black shades.

3. The water-soluble azo-dyestuff of the following formula:

H HOaS- N=N N\ n I GHQ-S0311 SOaH being" a black powder which dissolves in water to a grey-violet solution and dyes leather in the grain reddish-grey shades.

4. The water-soluble azo-dyestuif of the following formula:

being a black powder which dissolves in water to a violet-grey solution and dyes leather in the grain greenish grey shades.

ERICH FISCHER. WALTER GMELIN. RICHARD HUSS. 

